Mono- and polyazo dyestuffs containing a polyfluoroalkanol or a lower alkoxy polyfluoroalkyl



United States Patent 3,480,612 MONO- AND POLYAZO DYESTUFFS CONTAIN ING A POLYFLUOROALKANOL OR A LOWER ALKOXY POLYFLUOROALKYL Audley L. Cain, Amherst, N. assignor to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed May 18, 1966, Ser. No. 550,959 Int. Cl. C09b 45/32, 29/26; C07d 91/46 U.S. Cl. 260-146 Claims ABSTRACT OF THE DISCLOSURE Monoand polyazo dyestuffs containing a polyfluoro alkanol or alkyl ether group and their corresponding quarternary alkyl ammonium salts which are particularly useful as dyes for acrylic fiber in bright, attractive level shades with excellent fastness to light, washing and sublimation.

The present invention relates to novel mono and polyazo dyes and dyestuif intermediates. In a specific aspect thereof it relates to novel water-soluble quaternary alkyl ammonium dyestuffs suitable for coloring polyacrylonitrile fiber.

Since the introduction into commerce of yarn and textile containing polyacrylonitrile (hereinafter briefly referred to as acrylic fibers) much research effort has been devoted to the development of dyes for these synthetic fibers. It has been proposed to dye acrylic fibers with amino dyestuffs. These compounds are converted to their quaternary alkyl ammonium derivatives by treatment with a quaternizing agent such as dimethyl sulfate and applied to the fiber from aqueous solution. The resulting quaternized dyes, however, suffer from one or more of the following disadvantages:

(1) They exhibit low affinity for acrylic fiber.

(2) They produce dyeings of poor fastness to light, washing and sublimation.

(3) They dye acrylic fiber in dull unattractive shades.

(4) They produce dyeings of poor levelness.

It is therefore an object of the persent invention to provide new aminoazo dyestuffs which possess excellent fastness to light, washing and sublimation. A further object of the present invention is to prepare novel quaternary ammonium azo dyestufis which have excellent affinity for acrylic fiber and dye it bright, attractive level shades.

These and other objects and advantages will be apparent from the following description of the invention.

In accordance with the Present invention, new aminoazo dyestufis whose corresponding water-soluble quaternary alkyl ammonium salts dye acrylic fibers in bright, level, attractive shades fast to light, washing and sublimation are produced. The new azo dyestufi intermediates are represented by the structural formula:

wherein Q is the residue of a water-insoluble azo dyestuif and contains at least one radical of the group consisting of (a) a 2-benzothiazolylazo radical of the structure "ice in which Ph represents a 1,2-phenylene radical and (b) an amino-aryl azo radical of the structure in which R is an arylene radical selected from the benzene and napthalene series; R is a radical of the group which consists of hydrogen, lower alkyl (i.e. of 1 to 4 carbon atoms), lower cyanoalkyl, lower haloalkyl, and lower hydroxyalkyl; R and R are radicals which are each selected from the group which consists of lower alkyl, aralkyl, lower haloalkyl, lower hydroxyalkyl, lower cyanoalkyl, and which when taken together with the nitrogen to which they are attached, represent a heterocyclic ring; w is an integer having a value of 2 to 4; y is an integer having a value of 0 to 1, and Z is a substituent attached to an aromatic nucleus present in Q, said Z corresponding to the structure F R5 F X -(OFg),(E-J-l-(CF2)X4 2 o in wherein R is a radical selected from the group consisting of hydroxy and lower alkoxy; X X X and X; are halogens of atomic number 9 to 35, s and t are integers 0 to 1, and n is an integer having a value 1 to 2. Preferably X X X and X, are fluorine and s and t are 0.

The aromatic radicals, Ph and R in the above structural formulas may contain in addition to Z other simple substituents such as lower alkyl, lower alkoxy and ialogen.

The corresponding quaternary alkyl ammonium derivatives are represented by the structural formula,

and a quaternary alkyl ammonium arylazo radical of the structure:

(CH2) wy RI wherein Ph, R R R R n, w and y have the meanings given above, Z is a substituent of an aromatic nucleus of Q' and has the meaning given above, R is an alkyl group selected from the group a lower alkyl and aralkyl and A is a water-soluble inorganic or organic anion.

A preferred class of dyestuffs according to the present invention are monoazo dyestuffs of the structure.

Z-Ph wherein Z, Ph, R R w, y, R and R have the above assigned meanings and the corresponding quaternary alkyl ammonium salts thereof.

The monoand polyazo dyestuffs of the invention, which are represented by the formula QZ are prepared by diazotizing an amino of the structure s P \C-NH2 or of the structure R2 a NI-I -R N N i)wy R4 wherein Ph, R R R R w and y are as defined above, and coupling the diazotized amine with a coupling component wherein said amine, or said coupling component or both contain a Z group as defined above, as a substituent on an aromatic nucleus; or the instant novel azodyestuffs of the formula QZ are prepared by coupling a diazotized amine containing at least one aromatic nucleus with a coupling component of the structure wherein R is an aryl radical selected from the benzene and naphthalene series and R R R w and y are as defined above, and wherein the diazotized amine, or the coupling component, or both contain the group Z defined above, as a substituent on an aromatic nucleus.

The quaternary alkyl ammonium dyestuffs of the instant invention, represented by the formula Q (Z) +A are prepared by quaternizing the novel 2- containing azo-compound obtained from the above-described coupling reaction with an alkylating agent, or by coupling a diazotized amine with a coupling component as decribed above but wherein the coupling component has been quaternized. The instant novel dyestuffs in their unquaternized form are converted to the corresponding quaternary alkyl ammonium derivatives by treatment with conventional alkylating agents.

Suitable diazotizable amines containing Z wherein the substituent R according to the above structural formula is hydroxy can be prepared by admixing the appropriate haloketone with an aromatic amine in the presence of a sulfonic acid catalyst as is fully described in copending U.S. Patent application Ser. No. 329,889, filed Dec. 11, 1963, now U.S. Patent No. 3,405,177.

Suitable coupling components containing Z in which R is hydroxy can be prepared in accordance with the methods disclosed in French Patent 1,325,204 and copending U.S. patent application Ser. No. 327,520 filed Dec. 2, 1963, now U.S. Patent 3,324,185. Diazotizable amines and coupling component containing Z in which R represents a lower alkoxy group are novel compounds which can be prepared by treating the aforementioned diazotizable amines and coupling components with a conventional alkylating agent, e.g. dimethyl sulfate.

Typical amines which can be employed in preparing the novel dyestuffs include p-amino-alpha,alpha-bis(trifluoromethyl)-benzyl alcohol 4-amino-3,5-dimethyl-alpha,alpha-bis(chlorordifluoromethyD-benzyl alcohol p-amino-alpha,alpha-bis (trifluoromethyl) -b enzyl alcohol, methyl ether 2-aminobenzothiazole p-amino-2-chloro-alpha,alpha-bis (trifluoromethyl) benzyl alcohol 2-amino-alpha,alpha-bis(trifluoromethyl)-4-biphenyl methanol alpha,alpha-bis (trifluoromethyl) -p- (4'-amino-2',5'-

dimethoXy-phenylazo)-benzyl alcohol alpha,alpha-bis (trifiuoromethyl -p- 4'-arnino-2',5

dimethoXy-phenylazo)-benzyl alcohol, methyl ether 2-amino-alpha,alpha-bis(chloro-difluoromethyl)-6- benzothiazole methanol 4-amino-2-methyl-alpha, alpha-bis (chlorodifluoromethyl)-benzyl alcohol 4-amino-3-methoxy-alpha,alpha-bis(trifluoromethyl)- benzyl alcohol 4-amino-3-methoXy-alpha,alpha-bis(pentafluoroethyl)- benzyl alcohol 4-amino-3-ethoxy-alpha,alpha-bis(trifluoromethyl) benzyl alcohol 4-nitro-o-anisidine S-chloro-b-anisidine Z-ethoxyaniline aniline p-toluidine 2-amino-alpha,alpha-bis(trifluoromethyl)-6- benzothiazole methanol 2-amino-alpha,alpha-bis (trifluoromethyl)-6- benzothiazole methanol, methyl ether 2-amino-alpha,alpha-bis (chlorodifluoromethyl) -6- benzothiazole methanol, methyl ether Preferably, a Z-amino-benzothiazole containing the aforementioned group Z as substituent in the phenylene ring of the benzothiazole nucleus is employed and especially a 2 amino alpha,alpha bis(trifluoromethyl)-6- benzothiazole methanol. The aforementioned 2-aminobenzothiazoles containing Z are novel compounds which are readily prepared from anilines containing Z as a substituent of the benzene nucleus and having at least one position ortho to the amino group substituted with hydrogen.

The Z-containing 2-amino-benzothiazoles are prepared by conventional procedures for example by hologenating the reaction product of the aforementioned Z-containing aniline and an alkali metal thiocyanate in accordance with the procedure of U.S. Patent 2,773,054.

Typical coupling components which can be employed in preparing the novel dyestuffs of the invention include diethylaniline dimethylaniline trimethylanilinium metho-sulfate phenol anisole N,N-bis (beta-hyd roxyethyl m-toluidine N-ethyl-N-(beta dimethyl aminoethyl) aniline 2- N-ethyl-m-toluidine ethyl-trimethyl ammonium metho-sulfate 2-(N-[2-cyanoethyl]-m-toluidine)ethyl-thrimethyl ammoninum metho-sulfate N,N-dimethyl-2,S-dimethoxyaniline 2-(N-[2-methoxyethyl]-m-toluidine)ethyl-trimethyl ammonium metho-sulfate N-phenyl morpholine N-ethyl-N-(beta-chloroethyl)-m-toluidine N-(beta-cyanoethyl)-N-(alpha-hydroxypropyl)aniline N,N-bisbeta-hydroxyethyl -m-chloroaniline N-ethyl-N- beta-cyanoethyl aniline 2-(N-ethylanilino)ethyl trimethyl-ammonium metho-sulfate 4-dimethylamino alpha,alpha-bis(trifiuorornethyl)benzyl alcohol N,N-diethyl-alpha-naphthylamine N- lnaphthyl morpholine N-benzyl-N-ethylaniline 1 dimethylamino alpha,alpha bis(trifluoromethyl)-2- naphthalene methanol Preferably aryl amine and quaternary alkyl ammonium salts thereof which couple in the position para to the amino nitrogen are employed as coupling components.

Particularly good dyestuffs are obtained by employing a 2-(N-ethylanilino) ethyl trimethyl ammonium salt as the coupling component.

Dyestuffs containing two Z groups are obtained by coupling a Z containing diazotizable amine with a Z containing coupling component. For example,

is prepared by coupling diazotized p-amino-alpha, alphabis(trifluoromethyl)benzyl alcohol with 1-(N-methyl,N- dimethylaminoethylene) alpha,alpha bis (trifluoromethyl)-2-naphthalene methanol.

The quaternary ammonium derivatives of the aryl amine coupling components and aryl amino azo dyestuff-intermediates of the invention are prepared by known alkylation procedures, i.e. by reaction of the amine and an alkylating agent such as dimethyl sulfate; a lower alkyl chloride, bromide or iodide, benzyl chloride; methyl ptoluene sulfonate and the like. The quaternization reaction is advantageously effected in an inert organic diluent such as, o-dichlorobenzene, in order to obtain a fluid reaction medium.

The' anion A in the quaternary compound is an organic or inorganic Water soluble ion including Cl, Br, I HSO4 H2PO4", ZIlCl3 CH3SO3, C2H5SO3 C H SO HCOO", CH COO-, C H COO-, and the oxalate, tartrate and citrate ion.

The anion A- may be introduced by the alkylating agent, e.g. dimethyl sulfate (providing methosulfate anion) or the anion may be introduced in salting out the quaternary compound from the quaternization reaction mass for example by addition of zinc chloride (providing the trichlorozincate anion).

The quaternary monoand polyazo dyestuffs have excellent afiinity for acrylic fiber (either alone or in blends with other textile fibers) and dye it in attractive level shades fast to light, washing and sublimation. The lightfastness and/or levelness of the new quaternary dyes containing the group Z are in general superior to the lightfastness and/or levelness of quaternary dyes of analogous structure which contain negative substituents e.g. CH SO NO instead of Z. The quaternary dye's of the invention being water soluble are applied to acrylic fiber from acqueous solution preferably at the boil. Preferably the new dyes are applied from mildly acidic aqueous dyebaths of pH ca. 3 to 6.

The unquaternized amino azo dyestuff intermediates of the invention are water-insoluble dyes for synthetic hydrophobic fibers such as polyethylene terephthalate (Dacron), cellulose acetate and particularly super-polyamide fiber for example polyhexamethylene adipamide (nylon 66). The unquaternized amino azo dyes being water insoluble are applied according to the well-known disperse dyeing technique wherein the color is applied to the fiber from an aqueous dispersion of the dyestuff with the aid of a dispersing agent e.g. sodium lignosulfonate.

In the following examples which serve to illustrate the preparation of the novel dyes and dyestufi intermediates of my invention, parts are by weight unless otherwise noted and temperatures are in degress centigrade.

EXAMPLE 1 Part A Over a period of about 85 minutes a solution of 88 parts (0.55 mole) of bromine in 100 parts by volume of glacial acetic acid is charged to an agitated solution of 130 parts (0.5 mole) of p-amino-alpha,alpha-bis (trifluoromethyl) benzyl alcohol and 87 parts (1.1 moles) of sodium thiocyanate in 740 parts by volume of glacial acetic acid which is maintained at 25-35 C.

The reaction mass is agitated at ambient temperature for 24 hours and drowned in 6000 parts of water. A solution of 180 parts anhydrous sodium acetate in 2000 parts of water is added and the mixture is agitated for three hours at ambient temperature and filtered. The yellow solid which is collected is washed with water and dried in vacuo at 45-50". There is thus obtained 155 parts (98% of theory) of 2-amino-alpha,alpha-bis (trifluoromethyl)-6-benzothiazol-methanol (M.P. 285-289"; M.P. after recrystallization from aqueous methanol, 295- 297.2) of the structure:

Part B The product of Part A above is diazotized according to the following procedure:

Propionic acid (10 parts by volume) and acetic acid (20 parts by volume) are charged to a suspension of 6.4 parts (0.02 mole) of 2-amino-alpha,alpha-bis (trifluoromethyl)-6-benzothiazolemethanol in 10 parts by volume acqueous sulfuric acid which is maintained below 35. The resulting mixture is cooled to 10. Sodium nitrite (1.5 parts) is charged to 10 parts by volume of 95% sulfuric acid at 7075 and the resulting solution of nitrosyl sulfuric acid is cooled to 20 C. Over a ten minute period the nitrosyl sulfuric acid is added under agitation to the aminobenzothiazole solution which is maintained below -5 during addition. The reaction mass is agitated for 3 hours at 10 to -5. Over a period of one hour, 30 parts of water are charged to the mixture which is maintained below 0 during addition. Urea (1 part) is charged to the diazonium salt solution to destroy excess nitrosyl sulfuric acid.

EXAMPLE 2 Part A Dimethyl sulfate 30.1 parts (0.24 mole), is charged 0 a mixture of 63.2 parts (0.2 mole) of 2-aminoalpha, alpha-bis (trifluoromethyl)-6-benz0thiazolemetha nol (prepared as described in Example 1, Part A), 400 parts by volume ethyl alcohol (U.S. grade 2B) and 14 parts by volume 50 B. aqueous sodium hydroxide at 70. The mixture is heated at about 95 for two hours cooled to ambient temperature, drowned with agitation in 1000 parts of water and filtered. The yellow solid which is collected is washed with Water and dried in vacuo at 45- 50. There is thus obtained 64 parts (96% of theory) 2-amino-alpha,alpha-bis (trifluoromethyl) 6 benzothiazolemethanol, methyl ether having the structure:

After recrystallization from a mixture of 500 parts by volume of methanol and 300 parts of Water the product has a melting point of 321.2323.6.

Part B The product of Part A above is diazotized with nitrosyl sulfuric acid substantially as described in Example 1, Part B.

EXAMPLE 3 Part A A diazonium salt solution prepared from 6.4 parts of 2-amino-alpha,alpha-bis (trifluoromethyl -6-benzothiazole methanol as described in Example 1, Part B is charged to an agitated mixture of 3.9 parts (0.02 mole) of N,N-bis (beta-hydroxyethyl)m-toluidine, 3 parts by volume of aqueous 38% hydrochloric acid, 100 parts of Water and 50 parts of ice which is maintained at 0-5 during the addition. The coupling mass is agitated for about one hour at 0". A solution of 100 parts of sodium acetate in 500 This dyestuif when dispersed in water dyes Nylon 6,6 (polyhexamethylene adipamide) and cellulose acetate in attractive bluish red shades.

Part B The dystuif of Part A above (4 parts, 0.00765 mole) and 200 parts by volume of o-dichlorobenzene are agitated for 30 minutes at 150 to form a uniform slurry. Over a period of 5 minutes a solution of 0.87 part by volume of dimethyl sulfate in 8 parts by volume of o-dichlorobenzene is charged dropwise to the reaction mass which is maintained at 125-130 during addition. The mixture is heated at 125-130 for an additional two hours, cooled to ambient temperature, and filtered. The filter cake is washed with Skellysolve C (a petroleum hydrocarbon fraction boiling point 8898 Skelly Oil Co.) and agitated in parts by volume of methanol and 25 parts by volume of acetic acid to form a uniform slurry. After addition of 275 parts of water and a solution of 10 parts zinc chloride in 20 parts of water, the mixture is heated at 60 for 15 minutes, and cooled to ambient temperature. Sodium chloride (20 parts) is charged and the mixture is filtered The solid which is collected is dried in vacuo at 4550 C. There is thus obtained 3.8 parts of the dyestuff of the structure EXAMPLE 4 Part A A solution of 3 parts of dimethyl sulfate in 5 parts by volume of toluene is added to a solution of 3.84 parts (0.02 mole) of N-ethyl-N- (beta-dimethyl aminoethyl) aniline (prepared in accordance with the method described in U.S.P. 3,119,809) in 45 parts by volume of toluene at The mixture is heated at 95 for 30 minutes. After addition of 150 parts of water, the reaction mass is heated at 95 for an additional 15 minutes, cooled to ambient temperature and allowed to stratify. The lower aqueous layer containing 2-(N-ethylanilino)-ethyl trimethyl ammonium methosulfate is separated, diluted with 200 parts of water and cooled to 0.

Part B A diazonium salt solution which has been prepared from 6.4 parts (0.02 mole) of 2-amino-alpha,alpha-bis (trifluoromethyl)-6-benzothiazolemethanol by the procedure of Example 1, Part B above is added to the aqueous Z-(N-ethylanilino) ethyl trimethylammonium methosulfate which is agitated at about 0 during the addition. A solution of 150 parts of anhydrous sodium acetate in 500 parts of water is added to the coupling mass until the mixture is neutral to Dark Congo indicator. The reaction mass is agitated for 20 hours at 0 to 5 and heated to ambient temperature. Sodium chloride (50 parts) and a solution of 5 parts of zinc chloride in 10 parts of water are charged, precipitating a red tarry product. The supernatant aqueous liquor is decanted and the crude product is dissolved in 400 parts of water at and heated at with 1 part of Nuchar (adsorbent carbon, West Virginia Pulp and Paper Co.) for 15 minutes. The carbon is removed by filtration and the solution is cooled to ambient temperature. Sodium chloride (10 parts) and a solution of 5 parts of zinc chloride in 10 parts of water are charged and the mixture is agitated for 3 hours. The dyestuff which precipitates is recovered by filtration and dried in vacuo at 45-50". There is thus obtained 9.8 parts of a red watersoluble dyestuff corresponding to the structure The above color being ground with an equal weight of dextrin (an intermediate hydrolysis product of starch) dyes Orlon from an aqueous acetic acid bath in level brilliant yellow-red shades which are fast to washing and sublimation and particularly to light. Thus a 1% dyeing of Orlon of the color has a lightfastness of about 85 Standard Fade-O-Meter hours as measured by the procedure described in Technical Manual of The American Association of Textile Chemists and Colorists, 1962, p. B-61.

CH: CHgN(CH3)3 EXAMPLE 5 Part A According to the procedure of Example 3, Part A, the diazonium salt obtained from 12.8 parts 2-amino alpha,alpha bis (trifiuoromethyl) 6 benzothiazole methanol is coupled with 5 parts of dimethylaniline to provide 13.5 parts of the dyestuif having the structure This compound is an excellent red disperse dye for cellulose acetate, Nylon 6,6 and Dacron.

Part B A solution of 2.1 parts by volume of dimethylsulfate in 5 parts by volume of toluene is charged to an agitated solution of 8.8 parts of the above dyestuif in 300 parts by volume of toluene which is maintained at IOU-. The reaction mass is agitated for 24 hours at the latter temperature, cooled and filtered. The filter cake is washed with petroleum ether and dried in vacuo at 45-50 to provide 12 parts of a water-soluble dyestutf corresponding to the structure The above dycstufi after being ground with an equal weight of dextrin dyes Orlon from an aqueous acetic acid bath in an attractive level wash-fast reddish blue 3,480,612 9" 10 shade. The dyeing obtained has a lightfastness of about Part C 40 SFH as measured b the rocedur of Exa 1e 4.

- y p e mp A 8.6 part (0.02 mole) portion of the azo compound EXAMPLE 6 i is dissolved at 80 in a mixture of 50 parts by volume of Part A 5 acetic acid, 15 parts by volume of propionic acid, 10

parts by volume of 95% sulfuric acid and 10 parts of A parts ('025 mole) of water and diazotized with nitrosyl sulfuric substantially alpha'bls (mfluommethyl) benzyl alcohol m a mlxtum in accordance with the procedure of Example 1, Part B.

of 8 parts by volume of 20 B. aqueous hydrochloric O1 acid and 100 parts of water is diazotized at 0-5 by treatg g zgg gg gi ?3g i 5 3 1223 2 figi ment with a solutlon of 1.8 parts of sodlum nitrite in 15 10 ethyl m toluidino) ethyl trimethyl ammonium methosul parts of water fate by treatment with dimethylsulfate substantially in Part B accordance with the procedure of Example 4, Part A.

A 4 part sample (0.026 mole) of 2,5 dimethoxyaniline The diazonium salt solution and the quaternary salt is dissolved in a mixture of 200 parts of water and 5 are then coupled by a procedure analogous to that of Exparts by volume of B. aqueous hydrochloric acid and ample 4, Part B. The crude coupling product is recovered heated at 50-60 with 0.5 part Nuchar for 15 minutes. by filtration of the coupling mass, washed with 100 parts Afterremoval of the Nuchar by filtration the solution by volume of 5% aqueous sodium chloride and dried in is cooled to 0-5 and the diazonium salt solution is added. vacuo at 50-55. There is thus obtained 13.0 parts of a The coupling mass is agitated for one hour at 0-5" and 20 water soluble diazo-dyestulf corresponding to the strucbuffered by treatment with aqueous sodium acetate soluture OCH; (13F: /CH2CH3 JFQ (i) CH2CH2N(CH3)3 504C113 CH3 H3 tion as described in Example 4. The mixture is agitated The above color after being ground with an equal for two hours at 0-5, heated at 70 for 15-20 minutes, weight of dextrin colors Orlon fabric in an attractive cooled to ambient temperature and filtered. The orange washfast maroon shade of excellent levelness and good solid which is collected is washed with water and dried 4 lightfastness SFH). in vacuo at -50. There is thus obtained 10.2 parts (96% of theory) of an azo compound of the structure EXAMPLES 7 To 17 OCH: In several examples, procedures of drazothiation, CF; 1 coupling and quaternization analogous to. those employed HO g NH2 in the foregoing examples are employed in preparing the I 45 azo dyestuffs and quaternary derivatives thereof listed in 5 the table below.

Ex. Diazonium Component Coupling Component .Azo Dyestufi 7 Dia'zonlum Compound of Ex- Coupling component of Example 1, Part B. ample 6, Part. C.

s Diazonium Compound of Ex- Diethylaniline F s ample 2, Part B. CHSO C CN=N -N(C;H

9 Diazonium compound of Ex- N-phenyl morpholine i on S ample 1, Part B. HO CHzCHg CF: C-N= N\ /o Color of Color of Light- Ex Dyeing Quaternary Azo Dyestnfi Dyeing fastness 7 5 Red on Orlon 40 SEE.

no-o (Jim I C F CN=N N ZnCl;

N/ CH: CH2CH2N(CH3)3 CF3 8 I S Vlolet n Orlon. 40 SFH.

l C-N N N 02m): 2x1013- 0 Fa 9 F i S Blue on Orlon. 40 SFH.

HO, O /CH2OH2 C-N=N -N O SO4CH CFS CH2-CH2 Ex. Diazonium Component Coupling Component Azo Dyestufi C F; S 10 Diazonium Compound of N-ethyl-N-(beta-ohloro- CzH5 Example 1, Part B. ethyD-m-tolmdme. I C

0 F3 N- N N\ \N/ 6H CHzCHzCl 11 Diazonium Compound of Coupling component of Example 2, Part B. Exam e 4.

0 Fa s 12 Diazonlum Compound 02' Dielhylanilino V Example 1, Part B. HO O F a C --N=N N (C 2H5) z Color of Light- Ex. Dyeing Quaternary Azo Dyestufi Color of Dyeing iastness a S B /C2H5 ZnClr Violet on Orlon I CH2CH2C1 1? CH3 C H;

S 11 I 02115 ZnClr CHKO C Red on Orlon SFH.

C F a GN=N N\ N/ omommom):

I a S 12 HO"C Purple on Orlon SFH.

C-N=N -N(O2H5)2 ZnClr CFa l OII;

Ex. Diazonium Component Coupling Component Azo Dyestufi 13.. Diazonium Compound of Coupling Component of Example 6, Part A. Example 4.

14..." Diazonium Compound of Coupling Component of F S Example 2, Part B. Example 9. /CH2-CH \N CH -CH;

Diazonium Compound of N-(-beta-cyanoethyl)-N- (H113 S Example 1, Part B. (alpha-hydroxypropyD- CHzCHzCN aniline. I C F3 C-N=N -N\ omoHzomorr Color of Light- Ex. Color of Dyeing Quaternary Azo Dyestuti Dyeing iastness 13 C2115 Yellow on SFH.

Orlon. -N=N N ZnClr CF11 CH2CH2 a)a HO 0 14 .e Dark Blue SFH.

CFa S on Orion. CH3O C /CHzCH2 Cm C-N=N-N\ /0 solem- CH -CH 15.. Red on Nylon 6,6 and cellulose acetate Orange on Dacron.

Ex. Diazonium Component Coupling Component Azo Dyestufi 18,-.. Diazonium Compound of N,N-bis-(-beta-hydroxy- C F l S Example 1, Part B. ethyl)-rn-chl0ro-aniline. Ho

1 F C--N=N- N(CH:CHaOH)2 17--.. Diazonium Compound oi N-ethyl-N-(-beta-cyano-ethyl) C Fa S Example 1, Part B. aniline. I Glut HO-C (I) F CN=N-- --N\ CHnCHaCN Color of Light- Ex. Color of Dyeing Quaternary Azo Dyestufi Dyeing fastne'ss Red on nylon 6, 6 and cellulose acetate orange 0n Dacron v. Red on nylon 6, 6 and cellulose acetate I claim: wherein Ph represents a 1,2-phenylene radical or 1. An azodyestuft selected from the group consisting of: a lower alkyl, lower alkoxy or halogen substi- (I) an azocompound of the structure 5 tuted derivative thereof Q(Z) (b) and an amino-arylazo group of the structure n R R whereln Q is the resldue of a water-insoluble azo- 2 a dyestuff containing at least one radical selected from N=N R1 N the group consisting of: (CH2); y R4 z-befllolhlazqlylalo grouP thfi Structure in which R; is a member selected from the s group consisting of benzene, and naphthalene f or a lower alkyl, lower alkoxy or halogen suby stituted derivative thereof, R is a radical selected from the group which consists of hydrogen, lower alkyl, lower cyanoalkyl, lower haloalkyl and lower hydroxyalkyl, R and R are radicals each selected from the group which consists of lower alkyl, lower hydroxyalkyl, lower haloalkyl, lower cyanoalkyl, and which when taken together with the nitrogen to which they are attached, represent a heterocyclic ring, w is an integer having a value 2 to 4, y is an integer having a value to l, and Z is a substituent attached to said aromatic nucleus present in Q, said Z corresponding to the structure of the structure:

s Pg ;C N:N

N+ 1'1. and a quaternary alkyl ammonium arylazo radical of the structure:

R2 R3 -N=N-R N NR4 (0H2), y R

wherein Ph, R R R R n, w and y have the meanings given above, Z is a substituent of an aromatic nucleus of Q and has the meaning given above, R is selected from the group consisting of lower alkyl and benzyl and A- is a water-soluble anion. 2. An azodyestuff as defined in claim 1 wherein said R is benzene or a lower alkyl, lower alkoxy or halogen substituted derivative thereof.

3. An azodyestufi as defined in claim 1 wherein said Z has the structure and wherein R is a member selected from the group consisting of hydroxy and lower alkoxy. 4. An azodyestuif of the structure wherein R is a member selected from the group consisting of benzene and naphthalene or a lower alkyl, lower alkoxy or halogen substituted derivative thereof, R is a radical selected from the group which consists of halogen, lower alkyl, lower cyanoalkyl, lower haloalkyl, and lower hydroxya lkyl, R and R are radicals, each selected from the group consisting of lower alkyl, lower hydroxyalkyl, lower haloalkyl, lower cyanoalkyl, and which, when taken together with the nitrogen to which they are at tached represent a heterocyolic ring, w is an integer having a value 2 to 4, y is an integer having a value 0 to 1, Ph represents a 1,2-phenylene radical, and Z is a substituent attached to the aromatic nucleus of said phenylene radical, said Z corresponding to the structure X2 X3 wherein R is a radical selected from the group consisting of hydroxy and lower alkoxy, X X X and X; are each halogen selected, from the group consisting of fluorine, chlorine and bromine, s and t are are integers having the value of 0 to 1, and n is an integer having the value of 1 to 2.

5. An azodyestuif as defined in claim 4 wherein said Z has the structure wherein said R is as defined in claim 4.

6. A quaternary alkyl ammonium derivative of an azodyestulf as defined in claim 1 having the structure wherein Q is a residue of an azodyestufi containing as a water-solubilizing substituent at least one quaternary azoradical selected from the group which consists of an N- alkyl-Z-benmthiazoliumazo radical of the structure s Pg ;CN=N

N+ it. and a quaternary ammonium arylazo radical of the structure and wherein Ph, R R R R n, w, and y are each as defined in claim 1, Z is a substituent of an aromatic nucleus of Q and is as defined in claim 1, R is selected from a member of the group consisting of lower alkyl, and benzyl and A is a water soluble anion.

7. An azodyestulf as defined in claim 1 wherein said azocompound is of the structure where R is a 1,4-phenylene radical having up to two substituents on the benzene nucleus, said substituents being selected from the group consisting of methyl, methoxy and chloro, y is an integer as defined in claim 1, R and R are radicals each selected from the group consisting of methyl, ethyl, hydroxyethyl, chloroethyl, and when taken together with the nitrogen to which they are attached represent a morpholino ring, and R is a radical selected from the group which consists of hydroxy and methoxy and wherein said quaternary ammonium derivative of said azocompound is a water-soluble methyl ammonium salt.

8. An azodyestufi as defined in claim 1 of the structure wherein R is a 1,4-phenylene radical having up to two substituents on the benzene nucleus, said substituents salt.

9. An azodyestuif as defined in claim 1 wherein said azo dyestulf has the structure 0 Fa S H O /0 2 5 CHrCHzMCHa):

10. An azo dyestufi as defined in claim 1 wherein said azo dyestufi has the structure \N CHzCHzN (CH3)3 References Cited UNITED STATES PATENTS 1/ 1955 Dickey et al 260-496 X 12/1967 Fisher et a1. 260-158 XR FLOYD D. HIGEL, Primary Examiner US. Cl. X.R. 

